Water-based, solvent- and emulsifier-free microbicidal active compound combination

ABSTRACT

New microbicidal, optionally solvent- and emulsifier-free microbicidal active compound combinations and agents comprising known azole fungicides and quaternary ammonium compounds and their use in the preservation of materials.

This application is a continuation of application Ser. No. 08/202,715,filed on Feb. 23, 1994 now abandoned which is a continuation applicationSer. No. 07/942,554 filed on Sep. 9, 1992 now abandoned.

The present invention relates to new, in particular aqueous andoptionally organic solvent- and emulsifier-free microbicidal activecompound combinations comprising known azole fungicides and quaternaryammonium fungicides.

It is known that imidazole fungicides or triazole fungicides, such as,for example,α-[2-(4-chlorophenyl)-ethyl]-α-(1,1-dimethylethyl)-1-H-1,2,4-triazole-1-ethanol(tebuconazole),2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,3-triazol-1-yl)-propan-2-oland1-[[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl]-methyl]-1-H-1,2,4-triazole(propiconazole), can be used as such or in the form of their salts forprotecting plants and seeds (compare, for example, EP-A 0,040,345 andEP-A 0,052,424).

It is furthermore known that these compounds are also suitable for usein the preservation of materials for combating microbes which destroymaterials or discolour materials (compare, for example, DE-OS (GermanPublished Specification) U.S. Pat. No. 3,621,494 and U.S. Pat. No.4,079,062).

However, the azole fungicides, such as the tebuconazole mentioned, havegaps in their action on some germs relevant to the preservation ofmaterials, such as, for example, Trichoderma spec.

Because of the often low water-solubility of azoles, their use in somefields of application, such as, for example, leather, water-based woodpreservatives, disinfection, cooling water treatment, paper industry,metal processing and industrial preservation of water-containingproducts, is furthermore limited or impossible.

Quaternary ammonium salts have been known for a long time asmicrobicides having a broad action and are used, for example, indisinfection and preservation of textiles.

Although these active compounds are usually readily water-soluble, theytend to foam severely at the use concentrations, which causes trouble inmany fields of use. Furthermore, because of their cationic properties,they can react with anionic components, such as soaps, surfactants andthe like. This can adversely influence their profile of properties, orthey may become deactivated. It is furthermore known that quaternaryammonium salts can easily be deactivated by the presence of protein anddirt.

For many uses in the practice of preservation of materials, it isdesirable to employ the active compounds in liquid formulations whichare free from organic solvents or in which the corresponding solventcontent is drastically reduced.

Water-insoluble solvents are incompatible with aqueous products such asleather liquors, emulsion paints, cooling and process water anddisinfectants.

The users are often also not equipped to handle products in the form ofsolutions in organic solvents, since particular devices, associated withhigh investment costs, are necessary for application from the solventand for recovery thereof, which is essential to avoid ecologicalproblems.

Water-soluble solvents would in principle be suitable as solubilisingagents in aqueous systems. However, if they enter the waste water, theycan cause ecological problems. Furthermore, solvents can manifestthemselves adversely in the products to be preserved.

Another possibility of solubilisation for the preparation of water-basedactive compound formulations is to use emulsifiers. In the case ofhighly water-insoluble compounds, such as azoles, large amounts ofemulsifier are as a rule needed for this, which is to be avoided forecological reasons. The activity of the microbicidal active compound canlikewise be severely impaired by the use of emulsifiers. The usefulnessfor certain systems may also be limited.

The object of the invention was therefore to provide new, preferablywater-based, solvent- and emulsifier-free microbicidal active compoundformulations based on azole fungicides, which can be diluted easily withwater and then give storage-stable solutions for use.

It has now been found, surprisingly, that stable aqueous solutions oremulsions which have a particularly high microbicidal activity can beprepared by combination of at least one azole fungicide in the form ofthe free base, preferably

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazo-1-yl)-2-butanones(triadimefon)

β-(4-chlorophenoxy)-α-(1,1-dimethyl-ethyl)-1H-1,2,4-triazole-1-ethanol(triadimenol)

±α-[2-(4-chlorophenyl)-ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol(tebuconazole)

(RS)-2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)-hexan-2-ol(hexaconazole)

1-(N-propyl-N-(2-(2,4,6-(trichlorophenoxy)-ethyl)-carbamoyl)-imidazole(prochloraz),

2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol

1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolon-2-yl]-methyl]-1H-1,2,4-triazole(propionazole)

1-[2-(2,4-dichlorophenyl)-1,3-dioxolon-2-yl-methyl]-1H-1,2,4-triazole(azaconazole)

the isomers and isomer mixtures of the most diverse compositions alsobeing included in the cases where the compounds have asymmetric carbonatoms;

especially preferably±α-[2-(4-chlorophenyl)-ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol(tebuconazole)

and at least one quaternary ammonium fungicide, preferably of theformula (II) ##STR1## in which R¹, R², R³ and R⁴ are identical ordifferent and in each case represent unsubstituted or substituted,straight-chain or branched, saturated or unsaturated alkyl groups having1-20 carbon atoms, alkylaryl and aralkyl groups having 5-10 carbon atomsin the aryl part and 1-20 carbon atoms in the alkyl part or aryl groupshaving 5-10 carbon atoms, and optionally mono-or polyalkoxylatedderivatives hereof; possible substituents being halogen, C₁ -C₄ -alkyland C₁ -C₄ -alkoxy; and wherein 2 or 3 radicals R¹ to R⁴ on thequaternary centre, optionally with further hetero atoms, can form asaturated or unsaturated 5-, 6- or 7-membered (hetercyclic) ring and

X represents an anion which promotes water-solubility, such as, forexample, halide, sulphate, alkylsulphonate or optionally substitutedarylsulphonate.

Such aqueous formulations avoid the abovementioned ecological anduse-related disadvantages of solvent-based or emulsifier-mediatedformulations and in this respect are a useful enrichment of the priorart.

Quaternary ammonium compounds which may be mentioned as preferred areammonium salts such as

C₁₂ -C₁₄ -alkyl-benzyl-dimethylammonium chloride

trimethyl-coconut-ammonium chloride

didecyldimethylammonium chloride.

C₁₂ -C₁₄ -Alkyl-benzyl-dimethylammonium chloride is particularlypreferred.

As already mentioned, the azole fungicides are in the form of their freebase.

A combination of tebuconazoles and C₁₂ -C₁₄-alkyl-benzyldimethylammonium chloride is especially preferred.

The weight ratios of the active compounds in the active compoundcombinations can be varied within relatively wide ranges.

They depend in general on the field of use and on the particular azoleand guaternary ammonium fungicides employed. However, these weightratios can easily be determined in test series by simply mixing thecomponents.

The weight ratio of azole fungicide to quaternary ammonium fungicide ispreferably 1:99 to 99:1, in particular 1:40 to 9:1, particularlypreferably 1:20 to 1:1 and especially preferably 1:10 to 1:2. To prepareaqueous formulations, the active compounds are incorporated individuallyor as an active compound combination, for example in the form ofpowders, granules, pastes or concentrated solutions, suspensions oremulsions, into water by simple mixing, and are then present in the formof an aqueous suspension, solution or emulsion.

The aqueous solutions or emulsions preferably contain more than 20% byweight, in particular more than 40% by weight of water and can bediluted with water as desired to the use concentration. It is of coursealso possible for the active compounds or active compound combination inthe form of concentrates, solutions, suspensions, emulsions, powders,granules or pastes to be incorporated directly in the amounts requiredfor use, for example by stirring into the agent to be used.

The microbicidal agents contain the active compound combination in aconcentration of 0.001 to 95% by weight, in particular 0.01 to 60% byweight, and in addition optionally 0.001 to 30% by weight, in particular0.01 to 20% by weight, especially 0.05-10% by weight, of a suitableadditional fungicide, insecticide or an additional active compound.

The active compound combinations or agents according to the inventionhave a potent action against microorganisms. They are used in thepreservation of materials for preserving industrial materials; they areactive above all against moulds, wood-discolouring and wood-destroyingfungi and bacteria and against yeasts, algae and slime organisms. Thefollowing genera of microorganisms may be mentioned as examples--butwithout making a limitation:

Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillusniger and Aspergillus terreus, Aureobasidium, such as Aureobasidiumpullulans, Chaetomium, such as Chaetomium globosum, Cladosporium, suchas Cladosporium herbarum, Coniophora, such as Coniophora puteana,Gliocladium, such as Gliocladium virens, Lentinus, such as Lentinustigrinus, Paecilomyces, such as Paecilomyces varioti, Penicillium, suchas Penicillium brevicaule, Penicillium glaucum and Penicilliumpinophilum, Polyporus, such as Polyporus versicolor, Sclerophoma, suchas Sclerophoma pityophila, Streptoverticillium, such asStreptoverticillium reticulum, Trichoderma, such as Trichoderma virideand Trichophyton, such as Trichophyton mentagrophytes;

Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonasareuginosa, and Staphylococcus, such as Staphylococcus aureus; and

Candida, such as Candida albicans.

The amount of active compound combinations employed depends on thenature and the occurrence of the microorgnanisms of the germ count andon the medium. The optimum amount to be employed during use can bedetermined in each case by test series. In general, however, it issufficient to employ 0.001 to 20% by weight, preferably 0.05 to 10% byweight of the active compound mixtures, based on the material to bepreserved.

The new active compound combinations can be used as such or in the formof concentrates or generally customary formulations, such as powders,granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner which is knownper se, for example by mixing the active compounds with a solvents ordiluents, emulsifiers, dispersing agents and/or of binder or fixingagent, if appropriate siccatives and UV stabilisers and if appropriatedyestuffs and pigments as well as other processing auxiliaries.

Possible solvents or diluents are organochemical solvents or solventmixtures and/or a polar organic solvent or solvent mixtures and/or anoily or oil-like organochemical solvent or solvent mixture and/or waterwith at least one emulsifier and/or wetting agent. Customarywater-insoluble oily or oil-like solvents of low volatility which areused are, preferably, the particular mineral oils/solvent mixturescontaining mineral oils or aromatic fractions thereof. Examples whichmay be mentioned are white spirit, petroleum or alkylbenzenes, and inaddition spindle oil and monochloronaphthalene. The boiling ranges ofthese (mixtures of) solvents of low volatility spread over the rangefrom about 170° C. to not more than 350° C.

The oily or oil-like solvents of low volatility described above can bepartly replaced by organochemical solvents of higher volatility.

To prepare a wood preservative, some of the solvent or solvent mixturedescribed above is replaced by a polar organochemical solvent or solventmixture. Solvents which contain hydroxyl groups, ester groups, ethergroups or mixtures of this functionality are preferably employed here.Esters or glycol ethers may be mentioned as examples. Binders areunderstood according to the invention as binding drying oils orsynthetic resins which are water-dilutable or soluble, dispersible oremulsifiable in organochemical solvents, and for example those based onacrylic resins, vinyl resins, polyester resins, polyurethane resins,alkyl resins, phenolic resins, hydrocarbon resins or silicone resins.The binder used can be employed as a solution, emulsion or dispersion.Mixtures of alkyd resins and a drying vegetable oil are preferably used.Alkyd resins having an oil content of between 45 and 70% areparticularly preferred.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticiser (mixture). These additives are intended toprevent evaporation of the active compounds and crystallisation orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticisers originate from the chemical classes or phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stereate and amylstereate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether, or ketones, such as benzophenoneand ethylbenzophenone.

A possible solvent or diluent is preferably water, if appropriate mixedwith one or more of the abovementioned solvents or diluents, emulsifiersand dispersing agents.

According to the invention, industrial materials are non-livingmaterials which have been prepared for use in industry. Industrialmaterials which are to be preserved by active compounds according to theinvention against microbial change or destruction can be, for example,adhesives, sizes, paper and card, textiles, leather, wood, paints andarticles made of plastic, cooling lubricants and other materials whichmay be attacked or decomposed by microorganisms. Components ofproduction plants, for example cooling water circulations, which may beimpaired by multiplication of microorganisms may also be mentioned inthe context of the materials to be preserved. Preferred industrialmaterials in the context of the invention are adhesives, sizes, papersand cards, leather wood, paints, cooling lubricants, aqueous hydraulicfluids and cooling circulations.

The active compound combinations, agents or concentrates according tothe invention are preferably employed for preserving wood and timberproducts against microorganisms, for example against wood-destroying orwood-discolouring fungi, in particular in tropical wood preservation.

By wood which can be preserved by the mixtures according to theinvention there is to be understood, for example: building timber,wooden beams, railway sleepers, bridge components, boat jetties, woodenvehicles, boxes, pallets, containers, telephone poles, wooden fences,wood panelling, wooden windows and doors, plywood, chipboard, joinery ortimber products which are used quite generally in house construction orbuilding joinery.

Particularly effective preservation of wood is achieved by large-scaleimpregnation processes, for example vacuum, double vacuum- or pressureprocesses.

The activity and the action spectrum of the active compound combinationsaccording to the invention or the agents, concentrates or quitegenerally formulations which can be prepared therefrom is increased, ifappropriate, if other antimicrobially active substances, fungicides,insecticides or other active compounds are added to increase the activecompound spectrum or achieve particular effects, such as, for example,additional protection against insects. Particularly favourable mixingpartners are, for example, the following compounds:

sulphenamides, such as dichlofluanid (Euparen), tolylfluanid(Yethyleuparen), folpet or fluorfolpet; benzimidazoles (if appropriatein the form of their salts), such as carbendazim (MBC), benomyl,fuberidazole and thiabendazole; thiocyanates, such asthiocyanatomethyl-thiobenzothiazole (TCYTB) and methylene bisthiocyanate(MBT); morpholine derivatives, such as C₁₁ -C₁₄-4-alkyl-2,6-dimethylmorpholine homologues (tridemorph),(±)-cis-4-[3-tert.-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine(fenpropimorph) and falimorph; phenols, such as o-phenyl-phenol,halogenated cresols, tribromophenol, tetrachlorophenol,pentachlorophenol and 3-methyl-4-chlorophenol; dichlorophen;iodopropargyl derivatives, such as iodopropargylbutylcarbamate (IPBC),-chlorophenylformal, phenylcarbamate, hexylcarbamate andcyclohexylcarbamate; isothiazolinones, such asN-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one,4,5-dichloro-N-octylisothiazolin-3-one and N-octylisothiazolin-3-one(octhilinone); pyridines, such as 1-hydroxy-2-pyridinethione (and theirNa, Fe, Mn and Zn salts) tetrachloro-4-methyl-sulphonylpyridine andtetrachloro-4-methyl-sulphonylpyridine; metal soaps, such as thenaphthenate, octoate, 2-ethylhexanoate, olete, phosphate, benzoate andoxide of tin, copper or zinc; zinc salts of dialkyl-dithiocarbamates;tetramethyldiuram disulphite (TMTD);2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil); benzothiazoles,such as 2-mercaptobenzothiazole; thiazolyl-benzimidazole; quinolines,such as γ-hydroxyquinoline; benzyl alcohol mono(poly)hemiformal; andtris-N-(cyclohexyldiazeniumdioxy)-aluminium andN-(cyclohexyldiazeniumdioxy)-tributyltin.

Insecticides which are preferably added are:

phosphoric acid esters, such as azinphos-ethyl, azinphosmethyl,1-(4-chlorophenyl)-4-(O-ethyl,S-propyl)phosphoryloxy-pyrazole (TIA-230),chlorpyrifos, coumaphos, demeton, demeton-S-methyl, Diazinon,dichlorvos, dimethoate, ethoprophos, etrimfos, fenitrothion, fention,heptenophos, parathion, parathion-methyl, phosalone, phoxion, pirimiphosethyl, pirimiphos methyl, profenofos, prothiofos, sulprofos, triazophosand trichlorophone;

carbamates, such as aldicarb, bendiocarb, BPMC (2-(1-methylpropyl)phenylmethylcarbamate), butocarboxim, butoxycarboxim, carbaryl, carbofuran,carbosulphan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb,promecarb, propoxur and thiodicarb;

pyrethroids, such as allethrin, alphamethrin, bioresmethrin, byfenthrin(FMC 54 800), cycloprothrin, cyfluthrin, decamethrion, cyhalothrin,cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate,fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin,fluvalinate, permethrin and resmethrin; and nitroimides, such as1-[(6-chloro-3-pyridinyl)-methyl]-4,5-dihydro-N-nitro-1H-imidazol-2-anine(imidacloprid).

Possible other active compounds are algicides, molluscicides and activecompounds against "sea animals" which colonise on, for example, ship'sbottom paints.

The active compound combinations and agents according to the inventionadvantageously allow the microbicidal agents hitherto available to bereplaced by more effective and more environmentally compatible agents.They display a good stability and advantageously have a broad actionspectrum.

The following examples serve to illustrate the invention withoutlimiting it thereto. Parts and percentage data denote parts by weightand percentages by weight.

EXAMPLES

42.5 g of C₁₂ -C₁₄ -alkyl-benzyldimethylammonium chloride are initiallydissolved in 42.5 g of water. This solution is heated to 60° C. and 15 gof tebuconazole are added. The mixture is stirred at this temperatureuntil a clear solution is formed.

Example 2

5.5 g of a powder mixture consisting of 4.5 g of C₁₂-C14-alkyl-benzyldimethylammonium chloride and 1.0 g of tebuconazole arestirred into 94.5 g of water. A clear solution is obtained by stirringat about 60° C.

Example 3

42.5 g of C₁₂ -C₁₄ -alkyl-benzyldimethylammonium chloride are initiallydissolved in 42.5 g of water. This solution is heated to 60° C. and 10 gof tebuconazole are added. 5.0 g of iodopropargyl butylcarbamate arealso stirred into this clear solution and dissolved to form a clearsolution.

Example 4

30.0 g of C₁₂ -C₁₄ -alkyl-benzyldimethylammonium chloride are dissolvedand initially introduced into 30.0 g of water. 30.0 g of ethyl acetateare added to this solution and the mixture is homogenised by stirring.10.0 g of tebuconazole are stirred into the solution, which has beenheated to about 60° C., and are dissolved to form a clear solution.

We claim:
 1. A ready-to-use formulation comprising a fungicidallyeffective amount of a stable solution comprising:a)±α-[2-(4-chlorophenyl)-ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol(tebuconazole); b) iodopropargyl butylcarbamate; c) water; and d) C₁₂-C₁₄ -alkyl-benzyl-dimethylammonium chloride.
 2. A method of combatingfungi which comprises applying to said fungi or to a habitat from whichit is desired to exclude said fungi a fungicidally effective amount of aformulation according to claim
 1. 3. A method of protecting wood fromfungi which comprises applying to said wood a protective amount of aformulation according to claim
 1. 4. A method of protecting leather fromfungi which comprises applying to said leather a protective amount of aformulation according to claim
 1. 5. A concentrate intended to bediluted with water to form a ready-to-use fungicidical formulation, saidconcentrate comprising a fungicidally effective amount of a stablesolution comprising:a)±α-[2-(4-chlorophenyl)-ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol(tebuconazole); b) iodopropargyl butylcarbamate; c) water; and d) C₁₂-C₁₄ -alkyl-benzyl-dimethylammonium chloride.